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Abstract Reactive rhenium(III) nitride complexes could result from filling Re─N π* orbitals, but such complexes lie beyond the “nitrido wall” and are rare due to their instability. Here, we describe a method for bypassing the nitrido wall by incorporating a redox‐active isocyanide supporting ligand, which accommodates two electrons as shown by crystallographic, spectroscopic, and computational studies. These electrons can be returned to the metal during its facile reaction with CO to form a cyanate complex, demonstrating the nucleophilic reactivity of the nitride. Thus, assistance by the isocyanide enables an N2‐derived rhenium nitride to engage in N─C bond forming reactivity.
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A Low‐Valent Molybdenum Nitride Complex: Reduction Promotes Carbonylation Chemistry
Abstract Toward nitrogen functionalization, reactive terminal transition metal nitrides with high d‐electron counts are of interest. A series of terminal MoIVnitride complexes were prepared within the context of exploring nitride/carbonyl coupling to cyanate. Reduction affords the first MoIInitrido complex, an early metal nitride with four valence d‐electrons. The binding mode of the para‐terphenyl diphosphine ancillary ligand changes to stabilize an electronic configuration with a high electron count and a formal M−N bond order of three. Even with an intact Mo≡N bond, this low‐valent nitrido complex proves to be highly reactive, readily undergoing N‐atom transfer upon addition of CO, releasing cyanate anion.
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- Award ID(s):
- 1151918
- PAR ID:
- 10063019
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 57
- Issue:
- 31
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- p. 9670-9674
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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